Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2001-07-24
2003-05-27
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S287000, C526S307700, C526S318400
Reexamination Certificate
active
06569970
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for preserving a mineral molding by coating the surface of the mineral molding with an aqueous composition comprising an aqueous polymer dispersion whose dispersed polymer P comprises at least one ethylenically unsaturated acid and/or its conjugate base polymerized into it in free-radically polymerized form.
The present invention further relates to the mineral molding preserved according to the invention and to the aqueous polymer dispersion required for preservation according to the invention.
2. Description of the Background
In this document, a mineral molding is a molding produced from a mixture (a mortar) of a mineral binder, water, aggregates and, if desired, auxiliaries by, after shaping, the mineral binder/water mixture curing as a function of time, if desired under the action of elevated temperature. Mineral binders are generally known. They are finely divided inorganic materials such as lime, gypsum, clay and/or cement which are converted by mixing with water into their ready-to-use form, with the latter solidifying like stone as a function of time when left, in air or even under water, if desired under the action of elevated temperature.
The aggregates generally comprise granular or fibrous natural or synthetic rock (gravel, sand, mineral fibers), in special cases even of metal or organic aggregates or mixtures of the specified aggregates, having grain sizes or fiber lengths which are matched to the respective application in a manner known per se. Frequently, colored pigments are concomitantly used as aggregates for the purpose of imparting color.
Suitable auxiliaries are, in particular, those substances which accelerate or retard curing or influence the elasticity or porosity of the solidified mineral molding. These are, in particular, polymers as are known, for example, from U.S. Pat. No. 4,340,510, GB-B 15 05 558, U.S. Pat. No. 3,196,122, U.S. Pat. No. 3,043,790, U.S. Pat. No. 3,239,479, DE-A 43 17 035, DE-A 43 17 036, JP-A 91/131 533 and other documents.
Examples of the mineral moldings to be preserved according to the invention are concrete pipes as are used for the transport of sewage (cf., for example JP-A 55/44 273), concrete roofing tiles (cf., for example DE-A 21 64 256 or DE-A 39 01 073) or curb-stone, steps of stairways, floor slabs or baseplates on the basis of mineral binders.
A disadvantage of mineral moldings is that under the action of weathering (in particular the action of water) the cationic constituents such as Ca
2+
are leached out over the course of time, which reduces their strength. A further drawback of mineral moldings is the occurrence of efflorescence. This is presumably attributable to the fact that the mineral binders contain polyvalent cations such as Ca
2+
in an alkaline environment. Reaction with the carbon dioxide of the air can thus form sparingly water-soluble, ugly white lime spots on the surface of the mineral molding. The appearance of efflorescence can occur both during the curing of freshly prepared mineral moldings and also after the action of weathering on previously cured mineral moldings.
Attempts have long been made to counter the abovementioned draw-backs by sealing the mineral molding on its surface by application of a suitable coating.
Attempts were first made to preserve mineral moldings by coating with surface coatings based on vinyl chloride copolymers in organic solvents.
A disadvantage of this procedure is that it can be used only for dry mineral moldings since, on mineral moldings which are still moist, the adhesion of the surface coating is poor and, in addition, porous films are formed.
The abovementioned disadvantages of the organic surface coatings were relatively quickly overcome by sealing the surface of the mineral moldings by coating with aqueous compositions containing an aqueous polymer dispersion as film-former.
Dispersion polymers recommended for this purpose were styrene-acrylic ester copolymers, styrene-butadiene copolymers, homo-polymers and, in particular, copolymers or terpolymers of vinyl acetate with olefins, vinyl halides and/or (meth)acrylic esters, homopolymers or copolymers of vinyl propionate, (meth)acrylic ester homopolymers or copolymers, etc. (cf., for example DE-A 21 64 256, page 4).
However, the resulting coatings were not satisfactorily able to prevent the cationic constituents passing through. The Swiss Patent 446 720 recommends as a remedy the addition to the aqueous polymer dispersions of water-soluble salts or acids which form sparingly soluble salts with the cations of the mineral binders.
However, the action of these additives is limited since they are, for example, washed by rain from the films of the aqueous polymer dispersions as a function of time and thus only short-term protection is provided.
DE-A 39 01 073 and DE-A 38 27 975 recommend the preservation of mineral moldings by coating the corresponding surfaces with an aqueous composition containing as binder an aqueous polymer dispersion whose dispersed polymer contains from 0.5 to 5% by weight of at least one of the monomers acrylic acid, methacrylic acid, vinylsulfonic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid in free-radically copolymerized form.
A disadvantage of these coatings of mineral moldings is that their preservative action is not completely satisfactory.
It is an object of the present invention to provide an improved process for preserving a mineral molding, which does not have the disadvantages of the processes of the prior art.
SUMMARY OF THE INVENTION
We have found that this object is achieved by a process for preserving a mineral molding by coating the surface of the mineral molding with an aqueous composition which comprises an aqueous polymer dispersion whose dispersed polymer P comprises at least one ethylenically unsaturated acid and/or its conjugate base polymerized into it in free-radically polymerized form, wherein the polymer P of the aqueous polymer dispersion comprises at least one monomer of the general formula I
where the variables have the following meanings:
n is 0 to 2,
R
1
, R
2
, R
3
are, independently of one another, hydrogen or methyl,
X is oxygen or imino (NH) and
Y is hydrogen, alkali metal or ammonium,
polymerized into it in free-radically polymerized form.
Aqueous polymer dispersions whose dispersed polymer comprises at least one monomer of the general formula I polymerized into it in free-radically polymerized form are known and previously described, for example, in DE-A 25 24 064 where their films are recommended as pressure-sensitive adhesives. EP-B 95 695 recommends the use of aqueous polymer dispersions comprising at least one monomer of the general formula I polymerized into them in free-radically polymerized form for modifying hydraulically setting compositions. The same applies to EP-A 368 226. DE-B 19 32 395 recommends aqueous polymer dispersions comprising monomers of the general formula I polymerized into them in free-radically polymerized form for coating substrates different from mineral moldings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Monomers of the general formula I which are favorable according to the invention are:
Particularly suitable alkali metal salts of the monomers of the general formula I are the sodium and potassium salts.
Advantageously, the dispersed polymer P of the aqueous polymer dispersion to be used according to the invention contains, based on its weight, from 0.5 to 5, preferably from 0.5 to 2, particularly preferably from 0.5 to 1.5 and very from 0.5 to 1, % by weight of at least one monomer of the general formula I polymerized into it in free-radically polymerized form.
The polymer P to be used according to the invention is advantageously prepared by the method of free-radical polymerization, where suitable comonomers for the at least one monomer of the general formula I are monomers which are different from this and have at least one ethylenically unsaturated group. Suitable monomers of this type are,
Bäecher Reinhard
Bechert Bertold
Franzmann Gernot
Reck Bernd
Rehmer Gerd
Harlan Robert D.
Wu David W.
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